CN103842443A - Thermoplastic resin composition and molded article - Google Patents
Thermoplastic resin composition and molded article Download PDFInfo
- Publication number
- CN103842443A CN103842443A CN201280040012.6A CN201280040012A CN103842443A CN 103842443 A CN103842443 A CN 103842443A CN 201280040012 A CN201280040012 A CN 201280040012A CN 103842443 A CN103842443 A CN 103842443A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic resin
- phenol
- composition
- flame retardant
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 61
- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003063 flame retardant Substances 0.000 claims abstract description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 238000000465 moulding Methods 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 63
- 229920005610 lignin Polymers 0.000 claims description 52
- 125000003118 aryl group Chemical group 0.000 claims description 42
- 229920005668 polycarbonate resin Polymers 0.000 claims description 40
- 239000004431 polycarbonate resin Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000005027 hydroxyaryl group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- -1 poly(lactic acid) Polymers 0.000 description 44
- 238000000034 method Methods 0.000 description 33
- 150000002989 phenols Chemical class 0.000 description 27
- 239000000463 material Substances 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- 239000002023 wood Substances 0.000 description 9
- 229920000747 poly(lactic acid) Polymers 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 150000001896 cresols Chemical group 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920002522 Wood fibre Polymers 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- CFZAEHZKTCVBOQ-UHFFFAOYSA-N (2,3-dimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(OP(O)(O)=O)=C1C CFZAEHZKTCVBOQ-UHFFFAOYSA-N 0.000 description 2
- MUVQKFGNPGZBII-UHFFFAOYSA-N 1-anthrol Chemical compound C1=CC=C2C=C3C(O)=CC=CC3=CC2=C1 MUVQKFGNPGZBII-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229920000229 biodegradable polyester Polymers 0.000 description 2
- 239000004622 biodegradable polyester Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical group C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- KWQPWOQUXSQDNN-UHFFFAOYSA-N (2,3,4-trimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=C(OP(O)(O)=O)C(C)=C1C KWQPWOQUXSQDNN-UHFFFAOYSA-N 0.000 description 1
- BGGGMYCMZTXZBY-UHFFFAOYSA-N (3-hydroxyphenyl) phosphono hydrogen phosphate Chemical compound OC1=CC=CC(OP(O)(=O)OP(O)(O)=O)=C1 BGGGMYCMZTXZBY-UHFFFAOYSA-N 0.000 description 1
- GBZVNKQWXLVYNG-UHFFFAOYSA-N (3-phosphonooxyphenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=CC(OP(O)(O)=O)=C1 GBZVNKQWXLVYNG-UHFFFAOYSA-N 0.000 description 1
- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-UHFFFAOYSA-N 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- PKXYFOQKRMBDCQ-UHFFFAOYSA-N 2-phenylpropan-2-yl dihydrogen phosphate Chemical compound OP(=O)(O)OC(C)(C)C1=CC=CC=C1 PKXYFOQKRMBDCQ-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PEZYLGYHCJYONU-UHFFFAOYSA-N CC(C)C(C1=CC=CC=C1)(C(C)C)OP(=O)(O)O Chemical compound CC(C)C(C1=CC=CC=C1)(C(C)C)OP(=O)(O)O PEZYLGYHCJYONU-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
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- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
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- 239000004427 Tarflon Substances 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
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- 125000006267 biphenyl group Chemical group 0.000 description 1
- YKOQAAJBYBTSBS-UHFFFAOYSA-N biphenyl-2,3-diol Chemical compound OC1=CC=CC(C=2C=CC=CC=2)=C1O YKOQAAJBYBTSBS-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 210000004292 cytoskeleton Anatomy 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000035611 feeding Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- FTDXCHCAMNRNNY-UHFFFAOYSA-N phenol Chemical class OC1=CC=CC=C1.OC1=CC=CC=C1 FTDXCHCAMNRNNY-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 125000002444 phloroglucinyl group Chemical group [H]OC1=C([H])C(O[H])=C(*)C(O[H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention relates to a thermoplastic resin composition containing 100 parts by mass of a thermoplastic resin, (B) 1-40 parts by mass of a lignophenol having a specific structure, and (C) 0.5-30 parts by mass of a phosphorus flame retardant, and a molded article obtained by molding the thermoplastic resin composition.
Description
Technical field
The formed body that the present invention relates to thermoplastic resin composition and utilize it to form.More particularly, relate to by using life entity material, make its environmental performance good, and thermotolerance and flame retardant resistance good, in addition, also good thermoplastic resin composition and the formed body that utilizes it to form of molded appearance and humidity resistance.
Background technology
In recent years, from the viewpoint of environment protection, the life entity materials such as Biodegradable polyester resin receive publicity.As representational Biodegradable polyester resin, can enumerate poly(lactic acid).But common physical strength is low compared with the general-purpose plastics of life entity material and petroleum, and thermotolerance is also poor, its purposes is restricted in very narrow and small scope.
So, should expand the range of application of life entity material, by coordinate the petroleum polymkeric substance such as aromatic polycarbonate resin in poly(lactic acid), or carried out by coordinating the sponge that delignification processes in Biodegradable resin, attempt improving the physical strength (for example,, with reference to patent documentation 1 or 2) of resin-formed body.But the impact strength of these resin-formed bodies and thermotolerance are not necessarily enough high, can not fully meet basket and the desired characteristic of parts to household appliances, office furniture.
In the past, the inventor etc. are by coordinating the lignin phenol (lignophenol) with ad hoc structure in the polycarbonate resin to containing polycarbonate resin or poly(lactic acid), find environmental performance good, there is high workability and high-impact, the poly carbonate resin composition (with reference to patent documentation 3 and 4) of flame retardant resistance and excellent heat resistance simultaneously.But, when having coordinated the resin combination moulding of lignin phenol, occur that formed body is easily painted, and then the problem of the easy general silver color of formed body outward appearance.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-48067 communique
Patent documentation 2: TOHKEMY 2005-60556 communique
Patent documentation 3: TOHKEMY 2010-150424 communique
Patent documentation 4: TOHKEMY 2010-202712 communique
Summary of the invention
The problem that invention will solve
The object of the invention is, provides environmental performance good, and when suppressing painted when moulding, mobility, molded appearance, humidity resistance are good, and the extremely good thermoplastic resin composition of flame retardant resistance and the formed body that utilizes it to form.
The processes such as present inventor are carried out found that of wholwe-hearted investigation, by coordinating (A) thermoplastic resin, (B) lignin phenol of specified quantitative and (C) phosphorus flame retardant, painted can be inhibited moulding time time, mobility, molded appearance, humidity resistance are good, also extremely good thermoplastic resin composition and utilize its formed body forming of flame retardant resistance, has completed the present invention in addition.
, the invention reside in following thermoplastic resin composition and formed body are provided.
1. a thermoplastic resin composition, it is characterized in that, contain (A) thermoplastic resin 100 mass parts, (B) possess lignin phenol's 1～40 mass parts and (C) phosphorus flame retardant 0.5～30 mass parts of the structure that following general formula (I) represents.
(in general formula, R
1and R
4represent alkyl, aryl, alkoxyl group, aralkyl or phenoxy group, R
2represent hydroxyaryl or alkyl substituted hydroxy aryl, R
3represent hydroxyalkyl, alkyl, aryl, alkyl substituting aromatic base or-OR
5(R
5represent hydrogen atom, alkyl or aryl), the R beyond hydrogen atom
1～R
5can have respectively substituting group, p and q represent 0～4 integer.Be explained, p is 2 when above, multiple R
1can be identical or different respectively, in addition, q is 2 when above, multiple R
4can be identical or different respectively.〕
2. the thermoplastic resin composition as described in above-mentioned 1, wherein the thermoplastic resin of (A) composition comprises polycarbonate resin 40～100 quality % and polycarbonate resin thermoplastic resin 60～0 quality % in addition.
3. the thermoplastic resin composition as described in above-mentioned 1 or 2, wherein the phosphorus flame retardant of (C) composition does not contain halogen.
4. the thermoplastic resin composition as described in any one in above-mentioned 1～3, wherein the phosphorus flame retardant of (C) composition is phosphoric acid ester.
5. the formed body that the thermoplastic resin composition's moulding as described in any one in above-mentioned 1～4 is formed.
Invention effect
According to the present invention, be lignin phenol and phosphorus flame retardant by the life entity raw material that uses environmental protection, painted can be inhibited moulding time time, mobility, molded appearance, the thermoplastic resin composition that humidity resistance is good and flame retardant resistance is extremely good and the formed body that uses it to form.Especially while using polycarbonate resin as thermoplastic resin, when can obtaining good thermotolerance and shock-resistance, because the affinity of polycarbonate resin and lignin phenol is good, can as immiscible polymer alloy, not occur that peel off on the top layer of formed body, bad order.In addition, by improving life entity degree (vegetalization degree), can provide environment-protecting thermoplastic resin combination and the formed bodys thereof such as low carbon dioxide discharge capacity, low fossil feedstock.
Embodiment
Thermoplastic resin composition of the present invention is for containing (A) thermoplastic resin and (B) having the lignin phenol of ad hoc structure and (C) thermoplastic resin composition of phosphorus flame retardant.Below, each composition and other can be described by added ingredients.
[(A) thermoplastic resin]
As (A) thermoplastic resin in the present invention, can enumerate polycarbonate resin, phenylethylene resin series, polyvinyl resin, acrylic resin, plexiglass, polyvinyl chloride (PVC) RESINS, cellulose acetate resin, polyamide resin, vibrin (PET, PBT etc.), poly(lactic acid) and/or containing the multipolymer of poly(lactic acid), polyacrylonitrile resin, acrylonitrile-butadiene-styrene resin (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide (PPS), fluoro-resin, silicone resin, polyimide resin, polybenzimidazole resin, polyamide elastomer etc., and the multipolymer that forms of these and other monomer.
As (A) thermoplastic resin using in the present invention, from and (B) composition be the viewpoint of the affinity between lignin phenol, in preferred molecular structure, there is the thermoplastic resin of aromatic group, for example, aromatic polycarbonate resin, phenylethylene resin series, aromatic polyamide resin, aromatic polyester resins etc.
In addition, as (A) thermoplastic resin, by using polycarbonate resin, good shock-resistance and the thermotolerance that polycarbonate resin can be had are given obtained composition.Therefore, as thermoplastic resin, preferably use polycarbonate resin, or the mixture of polycarbonate resin and other thermoplastic resin.
Below to describing as the preferred polycarbonate resin of (A) thermoplastic resin.
(polycarbonate resin)
As the polycarbonate resin of (A) thermoplastic resin, it can be aromatic polycarbonate resin, also can be aliphatic polycarbonate resin, but as mentioned above, from and (B) viewpoint of the affinity between composition, and shock-resistance and stable on heating viewpoint, preferably use aromatic copolycarbonate tree.
< aromatic polycarbonate resin >
As aromatic polycarbonate resin, conventionally can use the aromatic polycarbonate resin making with reacting of carbonate precursor by dihydric phenol.Because aromatic polycarbonate resin is compared with other thermoplastic resins, thermotolerance, flame retardant resistance and shock-resistance are good, can be used as the main component of resin combination.
As dihydric phenol, can enumerate 4,4 '-dihydroxybiphenyl; 1,1-bis-(4-hydroxy phenyl) methane, 1, two (4-hydroxy phenyl) alkane such as 1-bis-(4-hydroxy phenyl) ethane and 2,2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane); Two (4-hydroxy phenyl) naphthenic hydrocarbon; Two (4-hydroxy phenyl) oxide compound; Two (4-hydroxy phenyl) thioether; Two (4-hydroxy phenyl) sulfone; Two (4-hydroxy phenyl) sulfoxide; Two (4-hydroxy phenyl) ketone etc.Wherein preferred dihydroxyphenyl propane.As dihydric phenol, can be a kind of homopolymer having used in these dihydric phenols, can be also to have used two or more multipolymers.In addition, can be also that multi-functional aromatics and dihydric phenol are also by the random branched polycarbonate resin of thermoplasticity obtaining.
As carbonate precursor, can enumerate carbonyl halides, haloformate, carbonic ether etc., specifically can enumerate two haloformates, diphenyl carbonate, methylcarbonate and the diethyl carbonate etc. of carbonyl chloride, dihydric phenol.
In the manufacturing processed of the aromatic polycarbonate resin using in the present invention, end terminator can be used as required, for example, the monohydric phenol compound that following general formula (II) represents can be exemplified as.
(in general formula, R
10the alkyl that represents carbon number 1～35, a represents 0～5 integer.)
The monohydric phenol compound representing as general formula (II), preferably para-orientation body.The concrete example of monohydric phenol compound can enumerate phenol, p-cresol, p-tert-butylphenol, to tert-octyl phenol, to cumyl phenol, nonylphenol and Pentaphen etc.These monohydric phenols can be distinguished use individually, also can use two or more combinations.
The aromatic polycarbonate resin that the present invention uses can have branched structure.Can use side chain agent in order to import branched structure, for example, can use and contain 1,1,1-tri-(4-hydroxy phenyl) ethane; α, α ', α "-tri-(4-hydroxy phenyls)-1,3,5-triisopropylbenzene; 1-(Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl)-4-(α ', and α '-bis-(4 "-hydroxy phenyl) ethyl) benzene; Three above compounds in the functional groups such as Phloroglucinol, trimellitic acid and isatin two (ortho-cresol) etc.
The viscosity-average molecular weight of aromatic polycarbonate resin that the present invention uses, from the physical property aspect of resin combination, preferably 10,000～40,000, more preferably 13,000～30,000.
In addition, in the present invention, as aromatic polycarbonate resin, using aromatic copolycarbonate-poly organo alkyl copolymer, or use in the situation of the material that contains aromatic copolycarbonate-poly organo alkyl copolymer, can further improve the shock-resistance under flame retardant resistance and low temperature.Form the organopolysiloxane of this multipolymer, consider from the angle of flame retardant resistance, preferably polydimethylsiloxane.
In the present invention, using polycarbonate resin, preferably aromatic polycarbonate resin is mixed with other thermoplastic resins while use, more than reaching 40 quality % with polycarbonate resin, preferably the mode of 50 quality % is used, and can maintain thus physical strength (shock-resistance, thermotolerance etc.).For polycarbonate resin, preferably mix other thermoplastic resins that use with aromatic polycarbonate resin, can from described (A) thermoplastic resin, select arbitrarily, but from the viewpoint of the mutual solubility of polycarbonate resin, preferred polyester resin (PET, PBT etc.), poly(lactic acid) and/or the phenylethylene resin series such as multipolymer, acrylonitrile-butadiene-styrene resin that contains poly(lactic acid).
[(B) lignin phenol]
(B) lignin phenol in the present invention has the structure shown in following general formula (I).
In general formula (I), R
1and R
4represent alkyl (the preferably alkyl of carbon number 1～4, be specially methyl, ethyl, propyl group etc.), aryl (the preferably aryl of carbon number 6～10, be specially phenyl etc.), alkoxyl group (preferably the alkoxyl group of carbon number 1～4, is specially methoxyl group, oxyethyl group, propoxy-etc.), aralkyl (the preferably aralkyl of carbon number 12～20, be specially phenmethyl etc.), or phenoxy group.
R
2represent hydroxyaryl (the preferably hydroxyaryl of carbon number 6～14, particularly, represent 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl etc.), or alkyl substituted hydroxy aryl (preferably the hydroxyaryl of carbon number 7～18, is specially 2-hydroxy-5-methyl base phenyl, 3-hydroxy-5-methyl base phenyl, 4-hydroxy-5-methyl base phenyl etc.); R
3represent hydroxyalkyl (the preferably hydroxyalkyl of carbon number 1～4; be specially hydroxymethyl, hydroxyethyl etc.); alkyl (the preferably alkyl of carbon number 1～4; be specially methyl, ethyl, propyl group etc.); aryl (the preferably aryl of carbon number 6～10; be specially phenyl etc.), alkyl substituting aromatic base (aryl that preferably alkyl of carbon number 1～10 replaces, is specially toluyl, xylyl etc.) or-OR
5(R
5represent the alkyl or aryl of hydrogen atom, alkyl, preferred carbon number 1～10, the aryl of preferred carbon number 6～10).
R beyond hydrogen atom
1～R
5can have respectively substituting group, p and q represent 0～4 integer.
Be explained, p is 2 when above, multiple R
1can be identical or different respectively, in addition, q is 2 when above, multiple R
4can be identical or different respectively.
In the present invention, the structure optimization that above-mentioned general formula (I) represents derives from natural structure.
In the case of deriving from natural structure, the R in above-mentioned general formula (I)
1and R
4determined R by seeds
1and R
4the substituting group representing is methoxyl group, and having p and q is respectively 1 or 2 structure, or exists only containing R
1and R
4the structure of one or both in the substituting group representing.
For example, conventionally, softwood tree is that the 3-that contains 1 methoxyl group replaces body, and the 3-that contains 1 methoxyl group in deciduous tree draft class plant replaces body and contains 3 of 2 methoxyl groups, and 5-replaces body and exists with the ratio of 1: 1.In addition, for any seeds and treelet, all may contain the structure not having as the part in the above-mentioned substituting group of methoxyl group.
R
3when deriving from natural structure, it is hydroxymethyl.
R
2when deriving from natural structure, with above-mentioned same, represent hydroxyaryl (the preferably hydroxyaryl of carbon number 6～14, be specially 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl etc.) or alkyl substituted hydroxy aryl (preferably the hydroxyaryl of carbon number 7～18, is specially 2-hydroxy-5-methyl phenyl, 3-hydroxy-5-methyl phenyl, 4-hydroxy-5-methyl phenyl etc.) etc.
In the present invention, by freely controlling the R that derives from natural structure
2, can increase the conversion of (B) lignin phenol.
The weight-average molecular weight polystyrene conversion of the represented lignin phenol of above-mentioned general formula (I), preferably 1,000～200,000, more preferably 3,000～100,000.The preferred phenol hydroxyl of two terminal group of the lignin phenol that in addition, above-mentioned general formula (I) represents.
In addition, the concrete structure representing as the above-mentioned general formula (I) of operable in the present invention (B) composition, can enumerate the wooden cresols structure that for example following general formula (III) represents.
(lignin phenol)
Lignin phenol is compound derivative in the xylogen being contained by timber, paper etc. and that come, and xylogen is to be for example filled between the gap of the carbohydrate for forming wooden cytoskeleton, the material working as intercellular adhesive.Because the structure of xylogen is very complicated, be not easy to use same as before, be transformed into lignin phenol and use of great use.
" B) manufacture method of lignin phenol)
(B) composition in the present invention can be by adding after phenol derivatives in the wood fibre such as timber, paper prime system material, lignin phenol and carbohydrate is isolated with acid hydrolysis.In addition, (B) composition contains the derivative of above-mentioned lignin phenol after alkaline purification, or contain hydroxyl in above-mentioned lignin phenol or the above-mentioned lignin phenol derivative after alkaline purification protected derivative.
The material that wood fibre prime system material is lignifying, is mainly the various materials as timber, for example, can be exemplified as that wood powder, wood are cut, waste wood and skirt materials etc.In addition, operable timber has any kind such as softwood tree, deciduous tree.In addition, also can use various herbaceous plant or relative material, for example, agricultural waste etc.
While using these material separation lignin phenols, preferably use the material obtaining without heating and pressurizing in sepn process.
As phenol derivatives, can use monohydric phenol derivative, diphenol derivative or trihydric phenol derivative etc.The concrete example of monohydric phenol derivative can be exemplified as phenol, naphthols, anthrol, oxanthranol etc., also can have respectively 1 above substituting group.The concrete example of diphenol derivative can be enumerated Resorcinol, Resorcinol etc., can have respectively 1 above substituting group.The concrete example of trihydric phenol derivative can be enumerated pyrogallol etc., also can have 1 above substituting group.
For example, contain the above-mentioned derivative composition in addition of enumerating such as hydroxyl anthracene, methoxyphenol (Dan Ersan), methyl catechol, biphenyl, dimethyl hydroxyl aryl, trimethylammonium hydroxyaryl and also can be used as phenol derivatives use.
The substituent kind that phenol derivatives can contain is not particularly limited, can contain any substituting group, but preferably electrophilic group (halogen atom etc.) group in addition, for example can enumerate alkyl (methyl, ethyl, propyl group etc.), alkoxyl group (methoxyl group, oxyethyl group, propoxy-etc.), and aryl (phenyl etc.) etc.In addition, in 2 ortho positions of the phenol hydroxyl on preferred phenol derivatives, have at least 1 not replace.The particularly preferred example of phenol derivatives is cresols, especially meta-cresol or p-cresol.
As acid, preferably Mierocrystalline cellulose there is the acid of swelling property.The concrete example of acid can be for example sulfuric acid more than concentration 65 quality % (for example, the sulfuric acid of 72 quality %), phosphoric acid more than 85 quality %, hydrochloric acid, tosic acid, trifluoracetic acid, Tricholroacetic Acid and formic acid more than 38 quality %.
As the extraction separating method of the lignin phenol obtaining as stated above, can enumerate for example following 2 kinds of methods.
The 1st kind of method is the method described in No. 2895087 communique of patent.Specifically, by wood fibre prime system material permeation liquid phenol derivativess such as wood powders, make xylogen solvation in phenol derivatives, then add concentrated acid and carry out dissolving lignocellulose based material.Now, the positively charged ion on the side chain α position of the basic structural unit of xylogen is by phenol derivatives attack, and the lignin phenol that has imported phenol derivatives in phenmethyl position generates mutually at phenol derivatives.Next be from phenol derivatives mutually extraction lignin phenol method.
For from phenol derivatives mutually extraction lignin phenol, undertaken by following manner: phenol derivatives is added in excessive ether, collects the throw out that obtains and be dissolved in again acetone.The part that is insoluble to acetone is removed by centrifugation, concentrated acetone-insoluble part.This part that is dissolved in acetone is splashed in excessive ether to collecting precipitation part.From this precipitation part except desolventizing, drying processing, obtain lignin phenol with the form that is dried thing.In addition, rugose wood element phenol is only removed phenol derivatives phase by underpressure distillation and is obtained.In addition, acetone-insoluble part also can be directly with the form of lignin phenol's solution, for the processing (alkaline purification) of derivative materialization.
The 2nd kind of method is the method as described in TOHKEMY 2001-64494 communique.Specifically following method: dissolved after the solvent of solid state or liquid phenol derivatives to permeating in wood fibre prime system material, distillation is except desolventizing (absorption process of phenol derivatives), then, adding concentrated acid to this lignocellulose based material dissolves cellulose components, identical with the 1st kind of method, lignin phenol phenol derivatives mutually in generate, extraction lignin phenol.
The extraction of lignin phenol can similarly be carried out with the 1st kind of method.Or use other following extracting process: will add in excessive water through concentrated acid total overall reaction liquid after treatment, collect insoluble part by centrifugation, dry after depickling.In this dry thing, add acetone or alcohol extraction lignin phenol.Next, this soluble part and the 1st kind of method are similarly splashed in excessive ether etc., lignin phenol obtains with the form of insoluble part.
The 1st or the 2nd kind of these two kinds of methods in, in the 2nd kind of method, especially the latter's extracting process, that is, and by the method for acetone or alcohol extracting and separating lignin phenol, so the few economy of the usage quantity of phenol derivatives.In addition, because the method can be processed a large amount of lignocellulose based materials with a small amount of phenol derivatives, thereby be applicable to a large amount of synthetic of lignin phenol.
(B) the of the present invention composition obtaining by aforesaid method generally has following characteristics.Be explained, the feature of (B) used in the present invention composition is not limited below.
(1) weight-average molecular weight is about 1,000～200, and 000.
(2) in molecule, substantially do not contain conjugated system, its tone is utmost point light color.
(3) derive from acerose fusing point and be about 170 ℃, the fusing point that derives from deciduous tree is about 130 ℃.
(4) result of phenol derivatives grafting selectively on side chain α position makes the amount of phenol hydroxyl very many, has been endowed the lignin derivative of height phenol characteristic.
(5) aromatic proton of lignin structure unit forms ditan type structure with the aromatic proton of the phenol derivatives in side chain α position grafting, suppresses from condensation.
(6) be easily dissolved in all kinds of SOLVENTS such as methyl alcohol, ethanol, acetone, diox, pyridine, THF (tetrahydrofuran (THF)), DMF (DIMETHYL FORMAMIDE).
In addition, (B) composition obtaining by aforesaid method uses after can deriving materialization by alkaline purification again.
The lignin phenol being obtained by phase separation process by natural lignin, the α position of its activated carbon is sealed by phenol derivatives, overall stability.But, under alkaline condition, the easy dissociation of its phenol hydroxyl, the β position carbon of the phenonium ion of generation possibility attack adjacency in solid.Like this, the aryl oxide bond rupture of β position, lignin phenol is by degraded, and then the phenol hydroxyl importing on phenol nucleus shifts to xylogen parent.Therefore, expect that through the derivative of alkaline purification hydrophobicity is better compared with lignin phenol before alkaline purification.
At this moment also expect to be present in the carbanion attack β position on alcoholate ion or the xylogen aromatic proton on the carbon of γ position, but the energy that this need to be high far away compared with phenonium ion.Therefore, expect under the alkaline condition relaxing, the adjacent group that imports the phenol hydroxyl of phenol core is preferentially embodied, under stricter condition, further react, the phenol hydroxyl regeneration of temporary transient etherfied cresols core, thus when making lignin phenol further degraded, because hydroxyl value increases, wetting ability has also raise.
In addition, lignin phenol and the lignin phenol's derivative after alkaline purification thereof are because the existence of phenol and alcohol hydroxyl group shows various characteristic.By protecting this hydroxyl, can obtain showing the derivative of other different qualities.The method of protection hydroxyl for example can be enumerated, for example, with protecting group protection hydroxyls such as acyl groups (can enumerate ethanoyl, propionyl, phenmethyl etc., preferably acyl group).In addition, by carrying out methylolation, produce new phenmethyl structure, can further expand its transition probabilities.
[(C) phosphorus flame retardant]
(C) phosphorus flame retardant in the present invention does not preferably contain the phosphorus flame retardant of halogen.If contain halogen, when the generation of obnoxious flavour while likely causing moulding, mould burn into burn formed body, the discharge of objectionable impurities, not preferred from the viewpoint of environmental pollution, security.
As not halogen-containing phosphorus flame retardant, there is not halogen-containing organic phosphorus flame retardant.As organic phosphorus flame retardant, if contain phosphorus atom and not halogen-containing organic compound, can use without particular limitation.Wherein, preferably use and contain 1 above and the phosphate compound of the ester Sauerstoffatom of phosphorus atom Direct Bonding.The phosphorus flame retardant that does not contain halogen beyond organophosphorus based compound has red phosphorus etc.
In addition, for phosphate compound, be not particularly limited, preferably not halogen-containing, the phosphate compound that for example following general formula (IV) represents.
(in general formula, R
11, R
12, R
13and R
14represent independently respectively hydrogen atom or organic group; X represents organic group more than divalence; M represent 0 or 1, n represent more than 1 integer; R represents more than 0 integer.)
In general formula (IV), organic group is for being substituted or not substituted alkyl, cycloalkyl, aryl etc.In addition, as the substituting group in substituted situation, there are alkyl, alkoxyl group, aryl, aryloxy, arylthio etc.In addition, these substituting groups are formed to such as aryl alkoxyalkyl of group forming etc., or the aryl sulfonyl aryl that these substituting groups are consisted of bondings such as Sauerstoffatom, nitrogen-atoms, sulphur atoms etc. also can be used as substituting group.
In addition, in general formula (IV), as organic group X more than divalence, refer to and can from above-mentioned organic group, remove the group more than 1 obtaining with the hydrogen atom of carbon atom bonding.For example, can enumerate alkylidene group, (replacement) phenylene, derive and next group from the bisphenols as multinuclear phenols.Preferably enumerate dihydroxyphenyl propane, Resorcinol, Resorcinol, ditan, dihydroxyl phenylbenzene and dihydroxy naphthlene etc.
Phosphate compound can be monomer, dimer, oligomer, polymer or these mixture.Specifically can enumerate trimethyl phosphate, triethyl phosphate, Tributyl phosphate ester, trioctylphosphine phosphoric acid ester, three butoxyethyl group phosphoric acid ester, triphenyl, trimethylphenyl phosphoric acid ester, tolyl diphenyl phosphoester, octyl group diphenyl phosphoester, three (2-ethylhexyl) phosphoric acid ester, diisopropylbenzyl phosphoric acid ester, three (xylyl) phosphoric acid ester, three (cumyl) phosphoric acid ester, three naphthyl phosphates, dihydroxyphenyl propane bisphosphate, Resorcinol bisphosphate, resorcinol diphosphate, Resorcinol-diphenyl phosphoester, trisphenol triguaiacyl phosphate, toluene diphenyl phosphoester, or their replacement body, polymkeric substance etc.
Herein, as commercially available not halogen-containing phosphate compound, can enumerate the TPP (triphenyl) that for example large eight chemical industrial companies manufacture, TXP (three (xylyl) phosphoric acid ester), CR-733S (Resorcinol two (diphenyl phosphoester)), CR-741 (phenol A bis-(diphenyl phosphoester)), PX-200 (1, 3-phenylene-tetra-(2, 6-3,5-dimethylphenyl) phosphoric acid ester), PX-201 (1, 4-phenylene-tetra-(2, 6-3,5-dimethylphenyl) phosphoric acid ester), PX-202 (4, 4 '-biphenylene-tetra-(2, 6-3,5-dimethylphenyl) phosphoric acid ester) etc.
[(A) thermoplastic resin, (B) lignin phenol and (C) mixing ratio of phosphorus flame retardant]
(A) thermoplastic resin, (B) lignin phenol and (C) mixing ratio of phosphorus flame retardant be, with respect to (A) composition 100 mass parts, (B) composition is 1～40 mass parts, and (C) composition is 0.5～30 mass parts.If (B) composition less than 1 mass parts can not obtain the effect that flame retardant resistance improves, if exceed 40 mass parts, painted effect step-down while suppressing moulding, not preferred.Preferably (B) composition is 2～30 mass parts.In addition, if (C) composition less than 0.5 mass parts, painted effect step-down while suppressing moulding, the easy general silver color of formed body, not preferred, in addition, can not further improve flame retardant resistance.In addition, if (C) composition exceedes 30 mass parts, the reduction such as thermotolerance, shock-resistance, not preferred.Preferably (C) composition is 2～20 mass parts.
[additive component]
Thermoplastic resin composition of the present invention is at interpolation (A) composition, (B) composition and (C) in composition, can add as required additive component.For example, phenol system, phosphorus system, sulphur are that antioxidant, static inhibitor, polymeric amide polyether block copolymer (giving permanent antistatic performance), benzotriazole system, benzophenone series UV light absorber, hindered amine are photostabilizer (weather agent), antiseptic-germicide, phase solvation, tinting material (dyestuff, pigment) etc.If the use level of additive component, in the scope of characteristic that keeps thermoplastic resin composition of the present invention, is not particularly limited.
[mixing and molding]
Thermoplastic resin composition of the present invention by by above-mentioned (A) composition, (B) composition and (C) composition according to the above ratio, in addition as required by the additive component of use by proper ratio coordinate, mixing forming.Cooperation now and mixing can be by using conventional apparatus, such as ribbon blender, drum-type rotary drum (drum tumbler) etc. carry out pre-mixing, then are undertaken by the method that uses Henschel mixer (Henschel mixer), Banbury (Bumbury mixer), single shaft screw extrusion press, twin shaft screw extrusion press, multiaxis screw extrusion press and pugging extruder etc.
Heating temperature when mixing can be according to the kind of thermoplastic resin, suitable selection in the scope of 200～350 ℃ conventionally, but use as thermoplastic resin in the situation of polycarbonate resin, in the scope of 240～300 ℃, select.
Thermoplastic resin composition of the present invention can pass through above-mentioned melting mixing forming machine, or take the particulate matter that obtains as raw material, manufacture various formed bodys by injection molding method, compression molding method, extrinsion pressing, blow molding method, extrusion forming method, vacuum forming and foaming method etc.Particularly preferably, by above-mentioned melting mixing method, manufacture granular shaping raw material, then utilize this particulate matter, manufacture injection-molded article by injection moulding or compression molding.
The present invention also provides a kind of formed body that thermoplastic resin composition's moulding of the invention described above is formed.
The formed body that thermoplastic resin composition's moulding of the present invention is formed, preferably injection-molded article (containing injection moulding compression) can be in frame, the various parts etc. of the OA machines such as duplicating machine, facsimile recorder, TV, receiving set, sound-track engraving apparatus, video recorder, computer, printing press, telephone set, information terminal, refrigerator, microwave oven, household appliances, electric and electronic apparatus.
Embodiment
The present invention illustrates by embodiment, but these do not have any restriction to the present invention.
The performance test of the resin combination obtaining in each example is performed as follows.
(1) melt index (MI): mobility
260 ℃ of condition determination resin temperatures, under load 21.18N, measure according to ASTM specification D-1238.
(2) heat-drawn wire (deformation under load temperature): thermotolerance
According to ASTM specification D-648, under load 1.8MPa, measure.Heat-drawn wire represents thermotolerance benchmark.
(3) oxygen index value (LOI): flame retardant resistance
Measure according to ASTM specification D-2863.Oxygen index value is that coupons maintains the value that the necessary minimum oxygen concentration of burning represents in airborne capacity %.
(4) yellowness index (YI): tint permanence
Make the formed body after 5 the 13rd material feedings, the spectrum colorimeter ∑ 90 that adopts Japanese electricity Se industrial to manufacture, by measuring area 30
, C2 light source transmission method measure and try to achieve its mean value.Represent the tint permanence of formed body.
(5) molded appearance
The tabular coupons (80mm × 80mm × 1mm) of molded appearance after by injection moulding at 260 ℃ of visual judgement mold temperatures has or not and occurs silver color.
Zero for not finding general silver color.
× for finding general silver color.
(6) humidity resistance
Humidity resistance is transferred horizontalization plate tensile sample sheet (80mm × 80mm × 1mm) by the environment of 60 ℃ of visual judgements, humidity 80% and is had or not surface deformation after 300 hours.
Zero for not finding surface deformation.
× for finding that surface is swelling, distortion.
(7) Ai Zuode impact strength (IZOD): shock-resistance
Used thickness is the coupons of 1/8 inch, according to ASTM specification D-256, measures measuring at 23 ℃ of temperature.
In addition, the each composition using in each example is as follows.
(A) thermoplastic resin
Polycarbonate resin: aromatic polycarbonate resin (trade(brand)name TARFLON A1700, bright dipping Xing Chan company manufacture, viscosity-average molecular weight=17,800)
Poly(lactic acid): trade(brand)name LACEA H100, Mitsui Chemicals, Inc. manufacture
ABS: amorphousness phenylethylene resin series (acrylonitrile-styrene-divinyl copolymer, trade(brand)name AT-05, Japanese A & L Zhu Shihui company manufacture)
(B) lignin phenol
The wooden cresols that above-mentioned formula (III) represents:
The wood powder of Buna (rubber) is immersed in the acetone soln that contains p-cresol, p-cresol is adsorbed on wood powder.The sulfuric acid vigorous stirring that wood powder after absorption adds 72 quality %.After stirring stops, adding the placement of purifying waste water, supernatant liquor is passed through to 6 decants operations repeatedly except disacidify and excessive p-cresol.Throw out in drying receptacle, adds acetone, and after the wooden cresols of the structure that extraction contains general formula (III), acetone is removed in distillation.Specifically, similarly carry out with the embodiment 1 of TOHKEMY 2001-64494 communique.
(C) phosphorus flame retardant
Dihydroxyphenyl propane two (phenylbenzene) phosphoric acid ester (trade(brand)name PX-200, large eight chemical industrial companies manufacture)
Triphenyl (trade(brand)name TPP, large eight chemical industrial companies manufacture)
[embodiment 1～7 and comparative example 1～9]
Coordinate above-mentioned each composition in ratio shown in table 1, supply with extrusion machine (machine title: VS40, Tian Bian plastics machinery company manufacture), melting mixing at 240 ℃, granulation.In addition, in all embodiment and comparative example, having coordinated respectively as phenol is IRGANOX1076 (BASF AG's manufacture) 0.2 mass parts of antioxidant and ADEKASTAB C (the ADEKA System of Co., Ltd.) 0.1 mass parts as phosphorous antioxidant.By the test portion sheet obtaining 120 ℃ dry through 12 hours after, under the condition of 260 ℃ of cylinder temperatures of injection moulding machine (Toshiba Machine Co. Ltd manufactures, pattern: IS100N), 80 ℃ of die temperatures, obtain coupons by injection moulding.The performance of the coupons obtaining by above-mentioned performance test evaluation, its result is as shown in table 1.
[table 1]
Learn as follows by table 1.
Embodiment 1～7
If to adding (B) lignin phenol and (C) phosphorus flame retardant in the polycarbonate resin as (A) thermoplastic resin, when YI and flame retardant resistance can be improved, molded appearance and humidity resistance are also good.
Comparative example 1～9
If use (B) lignin phenol and (C) phosphorus flame retardant when different, YI reduces (comparative example 1, comparative example 3, comparative example 5, comparative example 7, comparative example 9), can not realize high flame retardant (comparative example 1, comparative example 2, comparative example 4), thermotolerance reduces (comparative example 4, comparative example 6, comparative example 8), and molded appearance and humidity resistance be enough high (comparative example 1, comparative example 3, comparative example 4, comparative example 7) also.
Use possibility in industry
Thermoplastic resin composition of the present invention is by using life entity raw material wood element phenol and the phosphorus flame retardant of environmental protection, painted when the forming process occurring can prevent from using lignin phenol time, has good flame retardant resistance and thermotolerance simultaneously.And molded appearance, humidity resistance are also good.In addition, due to the environment-protecting thermoplastic resin combination such as output reduction, fossil feedstock minimizing of carbonic acid gas can be provided by use lignin phenol, therefore thermoplastic resin composition of the present invention goes for needing the field of these characteristics, especially electronic apparatus tool, information communication apparatus, OA apparatus, automotive field, building materials field etc.
Claims (5)
1. a thermoplastic resin composition, is characterized in that, contains:
(A) thermoplastic resin 100 mass parts,
(B) have structure shown in following general formula (I) lignin phenol's 1～40 mass parts and
(C) phosphorus flame retardant 0.5～30 mass parts,
In general formula, R
1and R
4represent alkyl, aryl, alkoxyl group, aralkyl or phenoxy group; R
2represent hydroxyaryl or alkyl substituted hydroxy aryl; R
3represent hydroxyalkyl, alkyl, aryl, alkyl substituting aromatic base or-OR
5, wherein R
5represent hydrogen atom, alkyl or aryl, the R beyond hydrogen atom
1～R
5can there is respectively substituting group;
P and q represent 0～4 integer, and wherein, p is 2 when above, multiple R
1can be identical or different respectively, q is 2 when above, multiple R
4can be identical or different respectively.
2. thermoplastic resin composition as claimed in claim 1, wherein,
(A) thermoplastic resin of composition comprises polycarbonate resin 40～100 quality % and polycarbonate resin thermoplastic resin 60～0 quality % in addition.
3. thermoplastic resin composition as claimed in claim 1 or 2, wherein,
(C) phosphorus flame retardant of composition does not contain halogen.
4. the thermoplastic resin composition as described in any one in claim 1～3, wherein,
(C) phosphorus flame retardant of composition is phosphoric acid ester.
5. a formed body, it is that the thermoplastic resin composition's moulding described in any one in claim 1～4 is formed.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2011-138874 | 2011-06-22 | ||
| JP2011138874A JP5843310B2 (en) | 2011-06-22 | 2011-06-22 | Thermoplastic resin composition and molded body |
| PCT/JP2012/065656 WO2012176778A1 (en) | 2011-06-22 | 2012-06-19 | Thermoplastic resin composition and molded body |
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| CN103842443A true CN103842443A (en) | 2014-06-04 |
| CN103842443B CN103842443B (en) | 2016-04-20 |
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| Country | Link |
|---|---|
| JP (1) | JP5843310B2 (en) |
| CN (1) | CN103842443B (en) |
| TW (1) | TW201300455A (en) |
| WO (1) | WO2012176778A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242539A (en) * | 2012-02-06 | 2013-08-14 | 富士施乐株式会社 | Lignophenol derivative, resin composition, and resin molded article |
| CN107735445A (en) * | 2015-07-29 | 2018-02-23 | 出光狮王塑料株式会社 | High reflection flame resistance thermoplastic resin compositions, formed body and lighting machine reflecting plate |
| CN113897023A (en) * | 2021-09-18 | 2022-01-07 | 北京嘉诚瑞鑫科技有限公司 | Non-metal automobile body environment-friendly covering piece and manufacturing method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9346922B2 (en) | 2013-11-26 | 2016-05-24 | International Business Machines Corporation | Flame retardant block copolymers from renewable feeds |
| US9284414B2 (en) | 2013-11-26 | 2016-03-15 | Globalfoundries Inc. | Flame retardant polymers containing renewable content |
| WO2017006986A1 (en) * | 2015-07-09 | 2017-01-12 | 出光ライオンコンポジット株式会社 | Resin composition and method for manufacturing same, and molded body |
| JP2020176213A (en) * | 2019-04-18 | 2020-10-29 | 清水建設株式会社 | Flame-retardant resin composition, molding and resin fiber |
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| CN1651478A (en) * | 2005-01-05 | 2005-08-10 | 福州大学 | Preparation of high boiling point alcohol lignin polyurethane |
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| JP3359718B2 (en) * | 1993-12-22 | 2002-12-24 | 株式会社竹中工務店 | Biodegradable resin composition |
| JP5572864B2 (en) * | 2008-12-25 | 2014-08-20 | 出光ライオンコンポジット株式会社 | Polycarbonate resin composition |
-
2011
- 2011-06-22 JP JP2011138874A patent/JP5843310B2/en not_active Expired - Fee Related
-
2012
- 2012-06-19 WO PCT/JP2012/065656 patent/WO2012176778A1/en active Application Filing
- 2012-06-19 CN CN201280040012.6A patent/CN103842443B/en not_active Expired - Fee Related
- 2012-06-21 TW TW101122284A patent/TW201300455A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651478A (en) * | 2005-01-05 | 2005-08-10 | 福州大学 | Preparation of high boiling point alcohol lignin polyurethane |
| CN1817994A (en) * | 2006-02-07 | 2006-08-16 | 福州大学 | Modified rosin resin with high-boiling point alcohol lignin and its derivative and production thereof |
| CN101130627A (en) * | 2006-08-23 | 2008-02-27 | 富士施乐株式会社 | Resin composition, resin molding, package, production method of resin molding and recycling method of resin molding |
| WO2010074228A1 (en) * | 2008-12-25 | 2010-07-01 | 出光興産株式会社 | Polycarbonate resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242539A (en) * | 2012-02-06 | 2013-08-14 | 富士施乐株式会社 | Lignophenol derivative, resin composition, and resin molded article |
| CN107735445A (en) * | 2015-07-29 | 2018-02-23 | 出光狮王塑料株式会社 | High reflection flame resistance thermoplastic resin compositions, formed body and lighting machine reflecting plate |
| CN113897023A (en) * | 2021-09-18 | 2022-01-07 | 北京嘉诚瑞鑫科技有限公司 | Non-metal automobile body environment-friendly covering piece and manufacturing method thereof |
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| Publication number | Publication date |
|---|---|
| CN103842443B (en) | 2016-04-20 |
| JP5843310B2 (en) | 2016-01-13 |
| TW201300455A (en) | 2013-01-01 |
| JP2013006911A (en) | 2013-01-10 |
| WO2012176778A1 (en) | 2012-12-27 |
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